Terminally modified, amino, polyether siloxanes

ABSTRACT

The present invention teaches the composition of terminally modified, amino, polyether, siloxanes, known henceforth as amino siloxane alkokylates, and their use as adjuvants. The amino siloxane alkoxylates of the present invention enhance the efficacy of agrichemicals on plants as compared to conventional TSE&#39;s alone. The amino siloxane alkoxylates have at one end, an amine functionality and at the other end, a polyalkyleneoxide functionality.

This is a continuation of application U.S. Ser. No. 09/209,061 filedDec. 10, 1998 now Pat. No. 6,238,684.

BACKGROUND OF THE INVENTION

Many herbicides require the addition of an adjuvant to the spray mixtureto provide wetting and spreading on foliar surfaces. Often that adjuvantis a surfactant, which can perform a variety of functions, such asincreasing spray droplet retention on difficult to wet leaf surfaces, orto provide penetration of the herbicide into the plant cuticle. Theseadjuvants are provided either as a tankside additive or used as acomponent in herbicide formulations.

Gaskin, et al., (Pestic. Sci. 1993, 38, 185-192) demonstrated that sometrisiloxane ethoxylates (TSE), such as Silwet L-77® surfactant(available from OSi Specialties, Inc. of Greenwich, Conn.), canantagonize cuticular penetration of a herbicide into grasses, whencompared to the herbicide alone. The term antagonism is used to indicatethat the treatment of herbicide plus adjuvant is less effective than thecomparative herbicide treatment.

Gaskin, et al., (Pest. Sci. 1993, 38, 192-200) showed that thisantagonism can be mitigated if the number of ethylene oxide (EO) unitscontained in the TSE is increased to 17 or more; however, superspreadingof the TSE is reduced dramatically once the degree of ethoxylationexceeds about 12 EO, and TSE's containing the higher EO adducts showspreading properties similar to conventional nonsilicone surfactants.

Sandbrink, et al., (Pest. Sci. 1993, 38, 272-273) published that a TSEantagonized glyphosate performance relative to glyphosate alone in thecontrol of Panicum maximum Jacq. Snow, et. al., Langmuir, 1993, 9,424-30, discusses the physical properties and synthesis of novelcationic siloxane surfactants. These siloxanes are based on the reactionof a chloropropyl modified trisiloxane with an alkanolamine, such asN-methylethanolamine, which was further reacted with a halide to make aquaternary surfactant.

Petroff, et al., (EP 92116658) describes the use of cationic, quaternarytrisiloxanes to enhance the efficacy of glyphosate on velvetleaf, abroadleaf weed. Henning, et al., (DE4318537) describes cationicsiloxanyl modified polyhydroxy hydrocarbon or carbohydrate for use withplant protection agents. These compounds are derived from a saccharidecontaining 1 to 10 pentose and/or hexose units, modified with aquaternary ammonium group, and a siloxane moiety.

Reid, et al., (U.S. Pat. No. 3,389,160) describes amino modifiedsiloxane alkoxylates where the amino functionality appears as theterminal group on the alkyleneoxide moiety, opposite the siloxane group.

Policello in PCT WO 97/32475 discloses amino modified siloxanes whereinthe amine is bound by an ether bond to the siloxane backbone wherein theamine may be terminal or pendant to the backbone.

SUMMARY OF THE INVENTION

The present invention teaches the composition of terminally modified,amino, polyether, siloxanes, known henceforth as amino siloxanealkokylates, and their use as adjuvants. The amino siloxane alkoxylatesof the present invention enhance the efficacy of agrichemicals on plantsas compared to conventional TSE's alone. Optionally, the amino siloxanealkoxylates of this invention may be blended with conventionaltrisiloxane alkoxylates. Blends of these unique amino siloxanes withmore traditional trisiloxane alkoxylates (TSA) provide superspreadingproperties, on difficult to wet surfaces, that are equal to, or greaterthan what is contributed by the individual components.

DETAILED DESCRIPTION OF THE INVENTION

These compositions are especially useful in overcoming the antagonisticeffects on pesticide efficacy associated with superspreading, TSAs.Mixtures of the compositions of the present invention with TSAs provideenhanced spreading properties relative to the individual componentsalone. In addition, these products provide a low aqueous surface tension(≦25 mN/m at 0.1 wt %), which is desirable for enhanced spreading ofpesticide solutions.

Composition

The amino siloxane alkoxylates of the present invention have the averagegeneral formula:

ZMe₂SiO[(Me)₂SiO]_(x) SiMe₂Q,

wherein x=0 to 2, preferably 1, Q=C_(a)H_(2a)O(C₂H₄O)_(b)(C₃H₆O)_(c)R,a=2 to 4, preferably 3, b=1 to 12, preferably 3 to 8, c=0 to 5,providing that when c is>0, (b+c)=2 to 12, preferable=4 and 8, R ishydrogen, acetyl or a hydrocarbon radical between 1 and 4 carbon atoms,Z is BN[DO(C_(d)H_(2d)O)_(e)R]_(2−Z)V_(z) each d is 2 to 4, preferably 2to 3, each e is 0 to 15, preferably 0 to 8, z=0 to 2, preferably 2, eachV is a univalent group, D is an alkylene divalent bridging group onwhich there may be hydroxyl substituents, and B is a divalent bridginggroup.

V groups preferably are alkyl (which may be branched, linear or cyclic)of less than 8 carbons, which may or may not contain hydroxylfunctionalities. Another preferred V is an alkyl amine functionality,the nitrogen of which may be further substituted (e.g. with an alkyl) orbe further alkoxylated. Exemplary V are ethyl, 2-hydroxyethyl,3-hydroxypropyl, methyl, and 2-aminoethyl.

B groups may be of the formula D(O)_(y)(C_(d)H_(2d)O)_(j)D wherein D andd are as above, j=0 to 8, preferably 0 to 2, and y=0 or 1. Preferably Dhas 2 to 6 carbon atoms. B may also preferably be a divalent alkylenegroup of C₂-C₄.

When Q or B is a mixture of oxyalkylenes, it may be blocked or random.One skilled in the art will understand the advantages in the position ofthe oxyethylene relative to the oxypropylene, when the alkyleneoxidegroup is blocked.

The Z groups may include protonated amines, i.e, where there is ahydrogen ion attached to the nitrogen in the Z group, which can occur tothe amino siloxane alkoxylates under acidic conditions. Alsocontemplated herein are quaternary versions of Z, i.e., where there is athird R³ group on the nitrogen in Z, but said quaternary compounds arenot preferred for use in the present invention.

Preferred Z structures are wherein R is hydrogen or methyl, D is adivalent organic group of 2 to 4 carbons, B is a divalent organic groupof 2 to 4 carbons, in which at least one carbon radical contains ahydroxyl group, and V is 2-hydroxyethyl, 2-hydroxypropyl,3-hydroxypropyl, propyl, ethyl or methyl. Preferred amino siloxanealkoxylates are trisiloxanes.

In addition the compositions of the present invention optionally mayinclude nonionic siloxane alkoxylates of the general formula:

R⁴Me₂SiO[MeSi(G)O]_(g)SiMe₂R⁴

wherein g=0 to 2, preferably 1.

G=C_(a)H_(2a)O(C₂H₄O)_(t)(C₃H₆O)_(w)R.

and R are as above, t=3 to 12, preferably 4 to 8

w=0 to 8, providing that when w is >0, (t+w) is preferably between 5 and12. R⁴ is G, or an alkyl of one to four carbons. The preferred nonionicsiloxane alkoxylates are trisiloxane alkoxylates, where g=1, d=3, t=4 to8, w=0, R⁴ is Me, R is H or Me.

The compositions of the present invention also optionally includeingredients for use herein are pesticides, especially acidfunctionalized ones, i.e., compounds that contain at least onecarboxylic, sulfonic or phosphonic acid group or their salt or ester.The term pesticide means any compound used to destroy pests, e.g.,rodenticides, fungicides, and herbicides. Illustrative examples ofpesticides which can be employed include, but are not limited to, growthregulators, photosynthesis inhibitors, pigment inhibitors, mitoticdisrupters, lipid biosynthesis inhibitors, cell wall inhibitors, andcell membrane disrupters. The amount of pesticide employed incompositions of the invention varies with the type of pesticideemployed. More specific examples of pesticide compounds that can be usedwith the compositions of the invention are: phenoxy acetic acids,phenoxy propionic acids, phenoxy butyric acids, benzoic acids, triazinesand s-triazines, substituted ureas, uracils, bentazon, desmedipham,methazole, phenmedipham, pyridate, amitrole, clomazone, fluridone,norflurazone, dinitroanilines, isopropalin, oryzalin, pendimethalin,prodiamine, trifluralin, glyphosate, sulfonylureas, imidazolinones,clethodim, diclofop-methyl, fenoxaprop-ethyl, fluazifop-p-butyl,haloxyfop-methyl, quizalofop, sethoxydim, dichlobenil, isoxaben, andbipyridylium compounds.

Manufacture

The amino siloxane alkoxylates of the present invention may be made bythe hydrosilation of a terminal hydridosiloxane with allyl glycidalether, and allyl started polyalkyleneoxide. This is followed by ringopening of the epoxide moiety with a primary or secondary amine. Thecomponents described are available commercially and may be made as knownin the art. Alternatively, the hydrosilation may take place with anallyl amine and an allyl started polyalkyleneoxide. Hydrosilationreaction conditions may be found in Marcienic, ed., 122-23 and 558-568(1995), which is incorporated herein.

The amine intermediate (e.g., allyl amine) may be prepared by reactionof an unsaturated halide (e.g., allyl bromide) and an amine. The allylamine also may be prepared by reaction of an allyl glycidyl ether (orsimilar unsaturated epoxide) with an amine (which result in an etherbond in the bridging group B). An alternative method uses aziridine,which is not preferred for toxicity reasons, are disclosed in PCTUS97/04128, which is incorporated herein by reference.

The hydrosilation products may be blends of the product of the presentinvention with amine terminated siloxanes and polyether terminatedsiloxanes. If desired, one may separate these, e.g., by distillation;however, these blends may be used without such purification.

The nonionic siloxane and the pesticides are available commercially andtheir manufacture is known in the art.

Use

The amino siloxane alkoxylates primarily are intended for use in theagricultural field as adjuvants for pesticide containing aqueousformulations. The composition of the present invention is useful as atank side additive, or as a component in a herbicide formulation. Inaddition the compositions of the present invention are useful asadjuvants for other pesticides, such as, fungicides, insecticides, plantgrowth regulators, acaracides and the like.

The siloxanes are added directly to a spray tank along with an acidfunctional pesticide, or as part of a pesticide formulation. When usedas a tankside additive, the amino siloxane alkoxylates are present atweight concentrations between 0.01% and 5.0%, preferably between 0.025%and 0.5%. Likewise, when the aminosiloxane alkoxylates are used in apesticide formulation (In-can), they are present at weightconcentrations that will deliver between 0.01% and 5.0% to the final usedilution, preferably between 0.025% and 0.5%, of the final use dilution.

It is noted that most dilutions will be made with water, but in the caseof crop oil concentrates, oils will be the diluents.

When the compositions of the present invention are used in conjunctionwith a nonionic siloxane alkoxylate, the weight ratio of the nonionicsiloxane alkoxylate to the amino siloxane alkoxylates is between 5:95and 95:5, preferably between 5:95 and 40:60. The blend may beaccomplished by physically mixing the two components together as aformulation, or by adding them separately to a spray mixture at point ofuse.

The amino siloxane alkoxylates also may be used generally as surfaceactive agents in aqueous formulation where there is an acidfunctionalized component. The amino siloxane alkoxylates of the presentinvention also may be used generally as surface active agents,including, but not limited to, surfactants, wetting agents and softenersfor textiles, as flowing and leveling agents in coatings, in hair careproducts, skin care and creams for personal care applications and asanti-static agents, detergents and softeners for laundry products. Otheruses will be obvious to those of skill in the art.

Optionally, the amino siloxane alkoxylates may be blended with othernonionic, cationic or anionic co-surfactants, especially those withhydrophobez of C₅-C₁₀ (short chain alkoxylates) and GEMINI surfactants(see WO 97/23281).

EXAMPLES

The following examples are presented to further illustrate and explainthe present invention and should not be taken as limiting in any regard.Unless otherwise indicated, all parts and percentages are by weight, andare based on the weight at the particular stage of the processing beingdescribed.

Example 1

a. Epoxy Siloxane Alkoxylates Intermediate:

25.0 g (0.1199 moles) of 1,1,3,3,5,5-hexamethyltrisiloxane (>97% by GC)was added to a 250 mL, 4 neck round bottom flask, equipped with amechanical agitator, a Claisen adapter containing a reflux condenser anda thermometer (with Therm-o-Watch), a nitrogen bypass, and a 100 mLaddition funnel containing 13.7 g, (0.1199 moles) of allyl glycidalether (AGE). The 1,1,3,3,5,5-hexamethyltrisiloxane was heated to 65° C.and catalyzed with 0.02 g of platinum catalyst. The AGE then was a addeddropwise to the reaction mixture which exothermic to a maximum of 72° C.The temperature was maintained by the addition rate of the AGE, andsupplemented as needed by a heating mantle. After all of the AGE wasadded, the temperature was adjusted to 80° C. At this point 10 g (0.0442moles) of allylpolyethyleneoxide (Allyl=18.2 wt %, Moles EO=4) was addedto the flask, along with an additional 0.03 g of platinum catalyst. Thereaction exothermed to 82.9° C. within 5 minutes. At this point thetemperature was adjusted to 90° C. and the remaining 25.24 g (0.1117moles) of allylpolyethyleneoxide was added dropwise from the additionfunnel to the flask contents. The temperature was maintained between 98°C. and 101° C. by the addition rate of the allylpolyethyleneoxide, andsupplemented, as needed, by a heating mantle. Once all of theallylpolyethyleneoxide was added, the temperature was adjusted to 95° C.and stirred for 1 hour. The reaction mixture showed no traces of SiHwhen introduced to a fermentation tube containing KOH/water/ethanolsolution. The product was cooled to 60° C. and treated with 4 g NaHCO₃,and stirred for 1 hour. The mixture was filtered through a fine filterpad and stripped on a Rotovap for 1.5 hours at 70° C. and 1.0 mm Hg toafford a clear amber liquid with an epoxy content of 6.0 wt % (92.4% oftheory based on initial charge).

b. Amino Siloxane Alkoxylate

The epoxy siloxane intermediate (55.0 g; 0.0825 moles), along with 11.28g (0.1073 moles) of diethanolamine (corresponding to an 30% molarexcess), and 28.4 g of 2-propanol (solvent), were added to a 250 mL. 4neck round bottom flask, equipped with a mechanical agitator, a Claisenadapter containing a reflux condenser and a thermometer (withTherm-O-Watch). and a nitrogen bypass. The mixture was heated to 80° C.,and catalyzed with 0.1 g titanium(IV) butoxide. The reaction time wasapproximately 6 hours, at which point the temperature was adjusted to50° C., and 0.5 g water was added to deactivate the catalyst. Mixingtime was approximately 1 hour. The product was then filtered through afine filter pad and stripped on a Rotovap for 1.5 hours at 70° C. and1.0 mm Hg to afford a clear amber liquid with a Brookfield viscosity of257 cps at 21° C. (spindle SG-2, 60 rpm).

The structure for the amino siloxane alkoxylate was confirmed by ²⁹Siand ¹³C NMR. The amino siloxane alkoxylate used here as an example, isshown as ASA-1, in Table 1. Other compositions of amino siloxanealkoxylates shown below were prepared according to this procedure.

Example 2

a. Composition Examples of Invention

Table 1 describe the amino siloxane alkoxylates used herein asillustrative examples of the compositions of the present invention.

TABLE 1 Description of Amino Siloxane Alkoxylates

Re- fer- ence X Q Group Z Group ASA- 1 C₃H₆O(C₂H₄O)₄HC₃H₆OCH₂CH(OH)CH₂NV₂ 1 ASA- 1 C₃H₆O(C₂H₄O)₅H C₃H₆OCH₂CH(OH)CH₂NV₂ 2 ASA-1 C₃H₆O(C₂H₄O)₅(C₃H₆O)_(2.5)H C₃H₆OCH₂CH(OH)CH₂NV₂ 3 ASA- 0C₃H₆O(C₂H₄O)₄H C₃H₆OCH₂CH(OH)CH₂NV₂ 4 V = —C₂H₄OH

b. Comparative Silicone Based Surfactants:

Table 2 provides structural information on two comparative trisiloxanealkoxylates that are commercially used as wetting agents foragrichemicals. These materials were prepared by standard hydrosilationof an allyl terminated polyether with an Si—H intermediate, such asheptamethyltrisiloxane. The SiH intermediates were prepared by acidequilibration as is known in the art.

TABLE 2 Description of Conventional Trisiloxane AlkoxylatesMe₃SiO[MeSi(G)O]₁SiMe₃ Reference G Group Sil-A C₃H₆O(C₂H₄O)₈CH₃ Sil-BC₃H₆O(C₂H₄O)₈H

c. Comparative Nonsilicone Surfactants:

Table 3 provides descriptions of typical, comparative, nonsiliconesurfactants, used as agricultural wetting agents.

TABLE 3 Description of Comparative Conventional Nonsilicone SurfactantsReference Moles EO Remarks OPE 10 Octylphenol ethoxylate (TRITON X-100)(Union Carbide Corp., Danbury, CT) TAE 15 Tallow amine ethoxylate(ETHOMEEN T/25) (Akzo Nobel Chemicals Inc.; Chicago, IL)

Example 3 Surface Tension

This example compares commonly used surfactants with the amino siloxanealkoxylate (ASA) compositions of the present invention for their abilityto provide a reduction of the aqueous surface tension to values ≦25mN/m, which is necessary for enhanced spreading, of pesticide solutions(Table 4). The aqueous surface tension was determined by the Wilhelmyplate method, using a sand blasted platinum blade as the sensor.Surfactant solutions (0.1 wt %) were prepared in 0.005 M sodium chloridesolution either alone or as mixtures. The mixtures of the ASA componentand SIL-B were prepared by blending 0.1 wt % solutions of the individualsurfactants at a ratio of 80/20 (ASA/SIL-B). Therefore,Blend-1=ASA-1/SIL-B, Blend 2=ASA-2/SIL-B, Blend-3=ASA-3/SIL-B, andBlend-4=ASA-4/SIL-B (all at a ratio of 80/20).

TABLE 4 Comparison of Surface Tension Properties Composition ofSurface^((a)) Surfactant Invention Tension ASA-1 Yes 23 ASA-2 Yes 24ASA-3 Yes 23 ASA-4 Yes 25 Blend-1 Yes 21 Blend-2 Yes 20 Blend-3 Yes 21Blend-4 Yes 20 Sil-A No 21 Sil-B No 21 OPE No 29 TAB No 41 None^((b))N/A 72 ^((a))Surface tension in mN/m at 25° C. ^((b))Surface tension ofwater from CRC Handbook of Chemistry and Physics; 63 Edition, 1982-1983.

Example 4

In addition the compositions of the present invention provide enhancedspreading when combined with nonionic trisiloxane ethoxylates, meaningthat the combination of the two components gives a greater degree ofspreading then either of the components alone, at concentrationsequivalent to that contained in the mixture (Table 5).

Spreading was determined by applying a 10 μL droplet of surfactantsolution to a polyester film (3M, IR 1140 transparency film) andmeasuring the spread diameter after 30 seconds. The solution was appliedwith an automatic pipette to provide droplets of reproducible volume.Deionized water that was further purified with a Millipore filtrationsystem was used to prepare the surfactant solutions.

To demonstrate the enhanced spreading observed with blends of the ASAcomponents of this present invention and traditional nonionictrisiloxane ethoxylates, 0.1 wt % solutions of each component wereprepared in distilled water. The solutions were blended in variousratios of the AMA component to SIL-B (See Table 5) to achieve thedesired blend composition. For example, a blend consisting of 9.0 gASA-1 (0.1 wt %) was combined with 1.0 g SIL-B (0.1 wt %) to afford amixture that contained 0.09 wt % ASA-1, plus 0.01 wt % SIL-B (a 90/10blend ratio). Likewise the comparative is SIL-B alone at concentrationsequivalent to what is contained in the corresponding blend. For example,the comparative blend with SIL-B for the 90/10 ratio, combines 9.0 gdistilled water with 1.0 g SIL-B. This yields 0.01 wt % SIL-B, which isequivalent to the amount contained in the 90/10 blend.

TABLE 5 Spreading Properties of Amino Siloxane Alkoxylate/SIL-B Blends(0.1 wt % Blend) Compara- tive Blend Ratio ASA-1 + ASA-2 + ASA-3 +ASA-4 + None + ASA/SIL-B SIL-B SIL-B SIL-B SIL-B SIL-B* 100/0 11  9  8nd NA 90/10 13 11 10 10  8 80/20 25 14 14 16 17 70/30 36 23 27 26 1760/40 30 33 30 32 28 50/50 45 41 30 36 34 40/60 44 44 44 nd 36 0/100 NANA NA NA 51 *None + SIL-B indicates that water was substituted for theASA component to provide spreading contributed by SIL-B.

Example 5

Nonionic trisiloxane alkoxylates have been shown to antagonize theuptake of glyphosate into grasses, giving a lower degree of uptake(Gaskin. et al., Pestic. Sci. 1993, 38, 185-192), or a lower degree ofcontrol then achieved with glyphosate treatments alone. The compositionsof the present invention provide enhanced glyphosate activity on grassesrelative to trisiloxane ethoxylates or glyphosate alone.

The effect of adjuvant on glyphosate isopropylamine salt (Gly-IPA)efficacy was determined using a barnyardgrass assay. Barnyardgrass(Echinochloa crus-galli) was crown in the lab under fluorescent growthlights, and trimmed 11 days after planting, from 9 cm to 4 cm. When theplants reached to 8-9 cm in height (3 days after trimming) they weretreated with spray solutions containing either glyphosate alone, or withglyphosate (Gly-IPA at 1.0%, 0.5% and 0.25%), plus a surfactant at 0.1wt %, using a spray volume of 96 l/ha. Efficacy was determined by visualobservation of plant regrowth 2 weeks after treatment, using a ratingsystem were 0 indicates no weed control, and 100% indicates completecontrol.

Table 6 provides the compositions for the various spray mixtures used totreat barnyardgrass in this example.

TABLE 6 Surfactant Composition for Spray Treatments Wt % Treatment AMA-1SIL-B Treatment-1 0.1 0 Treatment-2 0.08 0.02 Treatment-3 0.07 0.03Treatment-4 0.06 0.04 Treatment-5 0.05 0.05 Treatment-A 0 0 Treatment-B0 0.1

Table 7 demonstrates that the compositions of the present invention(Treatments 1-5 ) provide an overall significant enhancement toglyphosate response relative to glyphosate alone (Treatment-A), or tothe comparative trisiloxane ethoxylate SIL-B (Treatment-B).

TABLE 7 The Effect of Adjuvant on Glyphosate Efficacy on Barnyardgrass14 Days After Treatment Percent Barnyardgrass Control Glyphosate RateTreatment 1.0% 0.5% 0.25% Mean Treatment-1 77.5 a 42.5 b 36.3 a 52.1 aTreatment-2 38.8 b 75.0 a 36.3 a 50.0 a Treatment-3 80.0 a 42.5 b 23.3 a48.6 a Treatment-4 73.3 a 42.5 b 7.5 b 41.1 a Treatment-5 36.3 a 33.3 c5.3 b 24.9 b Treatment-A  8.7 c 28.0 c  1.0 b 12.3 c Treatment-B  8.8 c  5.0 d  3.0 b  5.6 c Data with different letters indicate astatistically different result. Data with common letters are notstatistically different according to Tukey test (p = 0.05).

Data with different letters indicate a statistically different result.Data with common letters are not statistically different according toTukey test (p=0.05).

Example 6

Barnyardgrass (BYG) was treated with glyphosate-isopropylamine salt(0.25%, 0.5% and 1.0%) using 0.1 wt % ASA-1, alone or as mixtures withSIL-B. The applications were made using a spray volume of 103 l/ha.Simulated rainfall (0.25 in.) was applied 2 h after treatment to removeany glyphosate that was not absorbed by the BYG. This was done todetermine how effective the treatments were at making glyphosaterainfast (resistant to wash-off), which is associated with the rapiduptake of chemical into the plants. Efficacy was determined by visualobservation of plant regrowth 2 weeks after treatment, using a ratingsystem were 0 indicates no weed control, and 100% indicates completecontrol.

Table 8 indicates that the ASA-1 and its blends with SIL-B are moreeffective at enhancing glyphosate efficacy on BYG than SIL-B. Asanticipated. SIL-B demonstrated the classical antagonism of glyphosateefficacy on grass species, when used with glyphosate rates below 1 wt %.However, even the treatment at 1 wt % glyphosate plus SIL-B, theenhancement in efficacy was not statistically different form glyphosatealone.

TABLE 8 Effect of Adjuvant on Glyphosate-IPA Efficacy on Barnyardgrass(2 Wks after treatment) % Glyphosate % ASA-1 1.0 0.5 0.25 100  99.5 a87.5 a 68.75 a 80 83.25 b 76.75 a 31.25 bc 70 92.25 b 60.0 a 32.5 bc 6092.0 b 77.5 a 17.5 c 50 92.5 ab 81.0 a 51.25 ab  0 57.5 c 7.5 b 8.75 c(100% SIL-B) 27.5 c 16.25 b 15.3 c No Surfactant Note: Mean followed bysame letter, within the same column, is not significantly different byTukey test (p = 0.05).

I claim:
 1. A composition comprising an amino siloxane alkoxylate of thefollowing formula: ZMe₂SiO((Me)₂SiO)_(x)SiMe₂Q wherein x=0 to 2,Q=C_(a)H_(2a)O(C₂H₄O)_(b)(C₃H₆O)_(c)R, a=2 to 4, b=1 to 12, c=0 to 5,provided that when c>0, (b+c)=2 to 12, R is hydrogen, acetyl, or ahydrocarbon radical having between 1 and 4 carbon atoms, Z isBN(DO(C_(d)H_(2d)O)_(e)R)_(2−z)V_(z), each d is 2 to 4, each e is 0 to15, z is 0 to 2, V is selected from the group consisting of alkyl ofless than 8 carbon atoms which may be optionally substituted withhydroxyl and alkylamine, the nitrogen of which may be optionallyalkoxylated or substituted with alkyl, D is an alkylene divalentbridging group of 2 to 6 carbon atoms on which there may be hydroxylsubstituents, and B is a divalent alkylene group of 2 to 4 carbon atomsor D(O)_(y)(C_(d)H_(2d)O)_(j)D, wherein j=0 to 6 and y is 0 or
 1. 2. Acomposition according to claim 1 additionally comprises an acidfunctional pesticide.
 3. A composition of claim 2 where the siloxane ispresent at a concentration between 0.01% and 95.0% by weight.
 4. Acomposition according to claim 3 where the acid functional pesticide isselected from, growth regulators, photosynthesis inhibitors, pigmentinhibitors, mitotic disrupters, lipid biosynthesis inhibitors, cell wallinhibitors, and cell membrane disrupters.
 5. A composition according toclaim 3 wherein the pesticide is an herbicide selected from the groupconsisting of: phenoxy acetic acids, phenoxy propionic acids, phenoxybutyric acids, benzoic acids, triazines, and s-triazines, substitutedureas, uracils, bentazon, desmedipham, methazole, phenmedipham,pyridate, amitrole, clomazone, fluridone, norflurazone, dinitroanilines,isopropalin, oryzalin, pendimethalin, prodiamine, trifluralin,glyphosate, glufosinate, sulfonylureas, imidazolinones, clethodim,diclofop-methyl, fenoxaprop-ethyl, fluazifop-p-butyl, haloxyfop-methyl,quizalofop, sethoxydim, dichiobenil, isoxaben, and bipyridyliumcompounds.
 6. A composition according to claim 1 additionally comprisinga nonionic siloxane of the formula R⁴Me₂SiO[MeSi(G)O]_(g)SiMe₂R⁴ whereing=0 to 2, G=C_(a)H_(2a)O (C₂H₄O)_(t)(C₃H₆O)_(w)R, t=3 to 12, w=0 to 8and R⁴ is G or an alkyl having one to four carbon atoms.
 7. Acomposition according to claim 6 wherein the weight ration of thenonionic siloxane to the amino siloxane alkoxylate is between 5:95 and95:5.
 8. A composition according to claim 6 wherein R⁴ is methyl.
 9. Acomposition according to claim 6 wherein g=1.
 10. A compositionaccording to claim 1 wherein Z is CH₂CH₂CH₂OCH₂CH(OH)CH₂N(C₂H₄OH)_(2.)11. A composition according to claim 1 wherein a=3, b=1 to 12, c=0 to 5,providing that when c>0, (b+c)=4 to 8, z=1 and V is an alkyl which maybe substituted with a hydroxyl functionality.
 12. A compositionaccording to claim 1 wherein a=3, b=1 to 12, c=0 to 5, providing thatwhen c>0, (b+c)=4 to 8, z is 1 or
 2. 13. A composition according toclaim 1 wherein a =3, b=1 to 12, c=0 to 5, providing that when c>0,(b+c)=4 to 8, b is D(O)_(y)(C_(d)H_(2d)O)_(j)D wherein j=0 to 6 and y is0 or
 1. 14. A composition according to claim 13 wherein, in the group Z,R is hydrogen or methyl, D is a divalent organic group of 2 to 4carbons, B is a divalent organic group of 2 to 4 carbons, in which atleast one carbon radical contains a hydroxyl group, and V is2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, propyl, ethyl ormethyl.
 15. A composition as in claim 1 wherein V is ethyl,2-hydroxyethyl, 3-hydrocylpropyl, 2-hydroxypropyl, methyl, ethyl, propylor 2-aminoethyl.
 16. A composition as in claim 7 wherein said weightration of nonionic siloxane to amino siloxane alkoxylate is between 5:95and 40:60.
 17. A composition as in claim 13 wherein j is 0 to
 2. 18. Acomposition according to claim 1 wherein the siloxane is blended withother nonionic, cationic or anionic co-surfactants.